Metallic halide thiourea compounds



United States Patent 3,210,278 METALLIC HALIDE THIOUREA COMPOUNDS JackRyer, East Brunswick, Paul M. Kerschner, Trenton, and Walter C.Bradbury, Newark, NJ., assignors to Cities Service Oil Company, acorporation of Delaware No Drawing. Filed Dec. 26, 1962, Ser. No.247,363 18 Claims. ((31. 252-46.4)

This application is a continuation-in-part of application Serial No.502, filed January 5, 1960, now abandoned.

This invention relates to new organo metallic compounds and moreparticularly to divalent metal halide organo metal complexes of thioureaand to a method for preparing the same.

There has been in recent years a growing interest in the combination oforganic radicals and metals to provide new and unique structures havinga variety of characteristics and properties which serve a multitude ofpurposes. New organo-metallic structures have been found particularlyuseful as catalysts, solvents, chemical intermediates, additives and inmany other applications.

The present invention is directed to a new series of compounds of thistype; more particularly metallic halidethiourea complexes having thegeneral structure wherein X is a halogen selected from the groupconsisting of chlorine bromine and iodine, M is a divalent metalselected from the gnoup consisting of zinc, cadmium and manganese, R andR represent a substituent selected from the group consisting ofhydrogen, alkyl having from .3 to 20 carbon atoms, alicyclic having from6 to 20 carbon atoms, amine substituted acyclic having from 2 to 11carbon atoms, aralkyl having from 7 to 20 carbon atoms, and aryl, and R"and R represent a substituent selected from the group consisting ofalkyl having from 3 to 20 carbon atoms, alicyclic having from 6 to 20carbon atoms, amine substituted acyclic having from 2 to 11 carbonatoms, a-ralkyl having from 7 to 20 carbon atoms, and aryl.

The divalent metal halide-thiourea compounds of the present inventionare prepared by first synthesizing an intermediate N, N or N, N, N, N,substituted thiourea which is thereafter reacted with a divalent metalhalide to produce a complex having the structure shown in the generalformula. Quite unexpectedly these new compounds have been found to bemost effective as extreme pressure additives when utilized in smallamounts in various lubricating compositions which include synthetic, aswell as mineral oil base lubricants.

In preparing lubricant compositions with the extreme pressure agents ofthe present invention it has been found that an amount of additive offrom 0.05% to about 15.0% by weight makes a most satisfactory lubricantcomposition. Preferably, the agent or extreme pressure additive will beused in an amount of from 0.1 to about 10% by weight of the baselubricant material. In preparing these new lubricant compositions, ithas been found that a wide variety of both mineral oil and syntheticbase stocks, including mixtures of the same, can be used. Suitablemineral oil base materials include 100 and 200 neutral oils, light andheavy intermediate mineral oils, bright stock and as well ascombinations of the foregoing. If a synthetic base material is useddiesters, polyesters, silicones, silicates, fluorocarbons, phosphates,polyglycols and polyphenyl ethers and mixtures of the same may be used.

3,210,278 Patented Oct. 5, 1965 In carrying out the preparation of theseextreme pressure compounds according to the method of this invention twomols of an amine are reacted with one mol of carbon disulfide in thepresence of a suitable hydrocarbon solvent such as benzene, toluene,xylene, propylbenzene or the like, under reflux conditions determined bythe particular solvent utilized. As the reaction between the amine andcarbon disulfide progresses hydrogen sulfide is evolved. The reaction iscompleted when hydrogen sulfide ceases to be evolved. The substitutedthiourea product obtained is dissolved in an alcohol solvent such asethanol, propanol, isopropanol, butanol, isobutanol, or the like, andheated to boiling. To this solution a hot alcohol solution of a selectedmetal halide is added. A substantially instantaneous reaction occursproducing a divalent metal halide substituted thiourea complex. Thelatter reaction is carried out in a molar ratio of approximately one molof substituted thiourea to one-half mol of the metallic halide. If thisreaction is not immediate on mixing, a gentle reflux may be applied at atemperature dependent on the solvent utilized. In selecting the latter,it is essential that the solution of the substituted thiourea and thesolution of the metallic halide be mutually miscible. If reflux iscarried out, either in the initial reaction leading to the preparationof the substituted thiourea or in the reaction of the latter with themetallic halide, periods of up to 12 hours or more may be necessary tobring about a completed reaction.

In preparing the substituted thiourea it has been found that aliphaticamines having from 3 to 20 carbon atoms, either straight chain orbranched chain, as well as cyclic, aromatic or substituted aromaticamines, or mixtures thereof may be used. The amine may be a primary orsecondary amine and may include unsaturation in a chain or ringstructure. Suitable amines for preparing the intermediate substitutedthiourea include the following: propylamine, butylamine, pentylamine,hexylamine, cyclo hexylamine, heptylamine, octylamine, nonylamine,decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine,pentadecylamine, hexadecylamine, benzylamine, heptadecylamine,octadecylamine, nonadecylamine, eisosanylamine, diethylamine,N-ethylpropylamine, dipropylamine, N-propylbutylamine, dibutylamine, N-butylpentylamine, dipentylamine, N-pentylhexylamine, dihexylamine,N-hexylheptylamine, diheptylamine, N- heptyloctylamine, dioctylamine,N-octylnonylamine, dinonylamine, N-nonyldecylamine, didecylamine,N-methylpentylamine, N-methylhexylamine, N-ethylpentylamine,N-ethylhexylamine, N-propylpentylamine, N-propylhexylamine,N-butylhexylamine, N-methylheptylamine, N ethylheptylamine,N-propylheptylamine, N-butylheptylamine, N-methyloctylamine,N-ethyloctylamine, N-propyloctylamine, N-butyloctylamine,N-pentyloctylamine, N-methylnonylamine, N-ethylnonylamine,N-propylnonylamine, N-butylnonylamine, N-pentylnonylamine,N-hexylnonylamine, N-methyldecylamine, N-ethyldecylamine,N-propyldecylamine, N-butyldecylamine, N-pentyldecylamine,N-hexyldecylamine, N-heptyldecylamine, phenylbutylamine, andN-octydecylamine. Lower molecular weight acyclic polyamines such asdi-N-butylaminopropylamine, ethylenediamine, diethylenetriamine,triethylenetriamine, and triethylenetetramine may be used.

In the foregoing general formula the amine residues are represented byR, R, R and R. These substituents may of course be similar or dissimilardepending on the amines selected in preparing the aminothiourea. If twomols of a primary amine are used, R and R will represent hydrogen with Rand R representing the residues of the amine chain. If secondary aminesof a mixture of secondary and primary amines are used, R, R, R and R'will represent the residues of the respective amines used.

The divalent metal halide selected for reaction with the substitutedthiourea will be a halide of a metal selected from the group consistingof zinc, cadmium and manganese. It is preferred that the halogen beeither chlorine, bromine or iodine. As previously indicated, a hotalcoholic solution of the divalent metal halide is prepared and reactedwith an alcoholic solution or equivalent solvent solution of thesubstituted thiourea. After this reaction has been completed excesssolvent is removed from the reaction zone by distillation. Traceresidues of unreacted thiourea may be removed from the reaction zone bydistillation under vacuum.

The examples which follow will provide a more complete understanding ofthe new compounds and their manner of preparation, as Well as thelubricant compositions in which these compounds are used.

EXAMPLE 1 To a one liter flask equipped with a stirrer, reflux condenserand dropping funnel, 398 gms. (2 mols) of Primene 81R (a Rohm & Haasmixed primary amine product) the residue formula of which is and 100 ml.toluene were added. 76 gms. (1 mol) of carbon disulfide was addeddropwise to the flask. The temperature was maintained in the range offrom 20 to 30 C. during addition of the carbon disulfide. After thecarbon disulfide was added, the mixture was refluxed at a temperature of100 i C. and maintained at this temperature for 12 hours. After thistime no further evolution of H 8 was noted. The reaction mixture wascooled to room temperature and the toluene solvent removed from thereaction flask by distillation with trace removal of toluene andunreacted amine being accomplished under vacuum. A 99.3% yield of thedesired compound S=C[NHC(CH (C H was obtained. One mol of this product(440 gms.) was dissolved in 50 ml. of isopropyl alcohol and heated toboiling. 68 gms. (0.5 mol) of zinc chloride, dissolved in a minimumamount of hot isopropyl alcohol, was slowly added with stirring to theboiling alcoholic disubstituted thiourea solution. The mixture wasallowed to cool to room temperature and excess isopropyl alcohol wasstripped by distillation from the reaction product complex. An 88% yieldof the complex was obtained. The compound is a liquid, reddish brown incolor and has a molecular Weight of 1016. An analysis of this compoundshowed 5.9% by weight of zinc and 5.3% by Weight of sulfur. Thecalculated weight percentage for zinc and sulfur are 6.4% and 6.3%respectively. The eifectiveness of this compound as an extreme pressureadditive is demonstrated in the table which follows wherein the compoundis identified as D.

EXAMPLE 2 Following the procedure set forth in Example 1dichlorobis-N,N'-dicyclohexylthioureazinc was prepared by first reacting198 gm. (2.0 mol) cyclohexylamine with 76 gm. (1.0 mol) carbon disulfidein the presence of ethanol and a small amount of potassium hydroxide.After evolution of hydrogen sulfide ceased excess ethanol was removedfrom the reaction zone by distillation. An isopropyl alcohol solution of68 gms. (0.5 mol) zinc chloride was added to a boiling isopropyl alcoholsolution N, N dicyclohexylthiourea. Excess alcohol was re moved from thereaction mixture leaving a light colored liquid product ofdichlorobis-N,N'-dicyclohexylthiourea zinc (Cl Zn[S=C(NHC H EXAMPLE 3Following the procedure set forth in Example 1dichlorobis-N,N'-di-n-butylthioureazinc was prepared by reacting twomols of n-butylamine with one mol of carbon disulfide to yield anN,N-di-n-butylthiourea intermediate which was thereafter reacted withone-half mol of an alcoholic solution of zinc chloride to yielddichlorobis- N,N n butylthioureazinc (Cl Zn(S C(NI-IC H This compoundhas a molecular weight of 512 and contained 12.9% zinc. Theefiectiveness of this compound as an extreme pressure additive isdemonstrated in the table which follows, wherein the compound isidentified as A.

EXAMPLE 4 Two mols of n-hexylamine were reacted according to the methodof Example 1 with one mol of carbon disulfide under reflux conditions inthe presence of approximately ml. of toluene until the evolution ofhydrogen sulfide ceased. The N,N' di nhexylthiourea obtained whenreacted with a hot isopropyl alcohol solution of zinc chloride yieldeddichlorobis N,N-di-n-hexylthioureazinc (Cl Zn[S=C(NHC H having amolecular weight of 616. This compound analyzed as followspercent zincby weight 9.7, percent sulfur by weight 9.2.

EXAMPLE 5 Two mols of di-n-butylaminopropylamine a Q) 2 2) a z) werereacted according to the method of Example 1 with one mol of carbondisulfide under reflux conditions in the presence of toluene until theevolution of hydrogen sulfide ceased. One mol of the N,N' di(di nbutylaminopropyl) thiourea obtained was reacted with a hot isopropylalcohol solution of one-half mol of zinc chloride to yielddichlorobis-N,N'-di-(di-n-butylarninopropyl) thioureazinc (ClgZXl[SC(NHC3H N(C4H9)2)2]2). compound has a molecular weight of 976 andanalyzed as follows:

Percent S: Found, 6.3; calculated, 6.6.

EXAMPLE 6 EXAMPLE 7 Two mols of dodecylamine were reacted according tothe foregoing examples with one mol of carbon disulfide under refluxconditions in the presence of toluene until the evolution of hydrogensulfide ceased. The N,N'-didodecylthiourea obtained was then reactedwith a hot isopropyl alcohol solution of zinc chloride to yielddichlorobis-N,N-di-dodecylthioureazinc having a molecular weight of 960,6.9% by weight of zinc and 6.2% by weight of sulfur. The calculatedvalues for this compound of zinc and sulfur are 6.8 and 6.7respectively. The compound is identified as B in the table whichfollows.

EXAMPLE 8 Two mols of Armeen-C (a mixed aliphatic amine prodnot of theArmour Co. having the formula were reacted according to the method ofExample 1 with one mol of carbon disulfide .under reflux conditionsuntil the evolution of hydrogen sulfide ceased. The mixed dialkylsubstituted thiourea obtained was reacted with a hot isopropyl alcoholsolution of zinc chloride in a molar 'ratio of 2:1 to yield a zincchloride complex of the mixed dialkyl substituted thiourea.

EXAMPLE 9 Two mols of phenylamine were reacted according to the methoddescribed in the foregoing examples with one mol of carbon disulfideunder reflux conditions in the presence of xylene until no furtherhydrogen sulfide evolution was noted. After removal of solvent analcohol solution of N,N'-diphenylthiourea was reacted with one-half molof zinc chloride to yield dichlorobis-N,N'-diphenylthioureazinc (C1 Zn[S=C (NHC H EXAMPLE 10 Two mols of oleylamine were reacted according tothe method of Example 1 with one mol of carbon disulfide under refluxconditions in the presence of toluene until the evolution of hydrogensulfide was completed. The N,N-dioleylthiourea obtained was thereafterreacted in the manner previously described with zinc chloride to yielddichlorobis-N,N'-dioleythioureazinc z 1a 35)2)2 This compound isidentified as C in the table following.

EXAMPLE 11 Two mols of Primene JM-T (a Rohm & Haas mixed aminecommercially available product having the following carbon chainstructure(C(CH (C H was reacted according to the method previouslydescribed with one mol of carbon disulfide to yield a disubstitutedthiourea. This intermediate was then reacted with an alcohol solution ofzinc chloride in a molar ratio of 2:1 to yield a dichlorothioureazinccomplex identified as compound E in the table.

EXAMPLE 12 Two mols of Primene 81R were reacted with one mol of carbondisulfide to yield an intermediate disubstituted thiourea which wasthereafter reacted with an alcoholic solution of cadmium chloride in themanner previously described to yield the dichlorocadmium complex of thedisubstituted thiourea. The product obtained 4.6% cadmium by weight and3.8% sulfur.

EXAMPLE 13 Two mols of Primene 81R were reacted with one mol of carbondisulfide to yield an N,N' disubstituted thiourea which was thereafterreacted in a molar ratio of 2:1 with manganese chloride according to themethod described above to yield the dichloromanganese complex of thedisubstituted thiourea. This product is identified as compound F in thetable.

EXAMPLE 14 To a one liter flask equipped with a stirrer, refluxcondenser and dropping funnel, 2 mols of Primene 81R and 100 ml. oftoluene are added. One mol of carbon disulfide is added dropwise to theflask. The temperature is maintained within the range of to C. duringthe addition of the carbon disulfide. After the addition, the mixture isrefluxed at a temperature of 100 i10 C. and maintained at thistemperature until reaction mixture is cooled to room temperature and thetoluene solvent is removed by distillation in vacuo with trace removalof toluene and unreacted amine. Two mols of this product is reacted withone mol of zinc bromide dissolved in a minimum amount of hot isopropylalcohol. The mixture is cooled to room temperature and excess alcoholstripped from the reaction product. The dibromozinc complex of thedisubstituted thiourea is thereby obtained.

EXAMPLE 15 To a one liter flask equipped with a stirrer, refluxcondenser and dropping funnel, 186 gms. (2 mols) of aniline and ml. oftoluene are added. 76 gms. (1 mol) of carbon disulfide are addeddropwise to the flask. The temperature is maintained within the range of20 to 30 C. during the addition of the carbon disulfide. After theaddition, the mixture is refluxed at a temperature of 100 :10 C. andmaintained at this temperature until no further evolution of H 8 isnoted. The reaction mixture is cooled to room temperature and thetoluene solvent is removed by distillation in vacuo with trace removalof toluene and unreacted amine. The compound is thereby obtained. Onemol of this product is reacted with 0.5 mol (63 gms.) of manganesechloride dissolved in a minimum amount of hot isopropyl alcohol. Themixture is cooled to room temperature and excess alcohol stripped fromthe reaction product complex. Dichlorobis-N,N-diphenylthioureamanganeseis thereby obtained. An analysis of this compound shows 10.5 percent byweight of manganese and 12.2 percent by weight of sulfur.

EXAMPLE 16 To a one liter flask equipped with a stirrer, refluxcondenser and dropping funnel, two mols (214 gms.) of benzylamine and100 ml. of toluene are added. One mol (76 gms.) of carbon disulfide isadded dropwise to the flask. During the addition, the temperature ismaintained within the range of 20 to 30 C. The mixture is refluxed at100 i10 C. until no further evolution of H 8 is noted. The reactionmixture is allowed to cool to room temperature and the toluene solventremoved by distillation in vacuo with trace removal of toluene andunreacted amine. The compound is obtained as a reaction product. One molof this compound is reacted With 0.5 mol (136 gms.) of cadmium bromidedissolved in hot isopropyl alcohol. The mixture is cooled to roomtemperature and excess alcohol stripped therefrom.Dibromobis-N,N-dibenzylthioureacadmium (Br Cd[S=C(NHCH C H 1 is obtainedas a reaction product.

EXAMPLE 17 Two moles (196 gms.) of cyclohexylamine in toluene arereacted with one mol (76 gms.) of carbon disulfide under refluxconditions. At the cessation of H 8 evolution, the mixture is allowed tocool to room temperature. One mol of the reaction product is reactedwith 0.5 mols (183 gms.) of cadmium iodide dissolved in a minimum amountof hot isopropyl alco-' hol. The mixture is cooled to room temperatureand excess alcohol stripped from the reaction product complex.Diiodobis-N,Ndicyclohexylthioureacadmium 2 s 11)2]2) is obtained as areaction product.

EXAMPLE 18 To a one liter flask equipped with a stirrer, refluxcondenser and dropping funnel, 2 mols (262 gms.) of N', N"dimethyldiethylenetriamine and 100 ml. of toluene are added. One mol (76 gms.)of carbon disulfide is added dropwise at a temperature of 20 to 30 C.The mixture is refluxed until no further H 8 evolution is noted. Thereaction mixture is cooled to room temperature and the toluenesubsequently removed. The reaction product obtained has the formula [hcNH c H NHc HrN(C s)21z One mole of this compound is reacted with 0.5 mol(68 have been demonstrated to have increased load carrying properties.

Typical examples of these oils including the specific amounts ofadditive to provide the improved load carry- 5 ing characteristics willbe apparent from the table which 0f Zlnc chloflde dissolved in hot P PYalcofollows wherein data is provided on the test results car- 1101. Th6IniXtllTe is cooled room temperature and ried out in a standard Shell 4ball test procedure. excess alcohol pp therefrom The complex Thestandard Shell 4 ball test is based on the use of chlol'obis s y y l anapparatus that includes 3 rigidly held /2" metal balls realiflc) 2 2 4 24 3)a)2]2 is 10 (type 52-100 steel balls) submerged in the lubricant toObtain d as a rea tion p odu t. be tested in a metal cup. A 4th ball ofthe same size EXAMPLE 9 and material is pressed into contact with the 3fixed balls by an adjustable loading arm and allowed to rub overAccordlng to the Procedures Ex'ample W mol a fixed period of time. Thecontact points on the 3 (129 gms-) of N'propylamlflamme 1S reacted g 15stationary balls grow to circular scars as Wear progresses. mol (38 ofcarbon dlsulfide Produce The average diameter of these scars in mmsafter the propylamylthiourea. 0.5 mol 0f th P d 15 reacted fixed periodof operation at a particular speed and load f 025 .gmsJ of P- bromlfieto Produce is taken as a measure of wear. The temperature at whichdlbmmobls'NrN 'dlpropylamylthloureacadmlum the test is carried out maybe varied from room tempera- (B Cd[S::C(N(C I-I )(I l-1 0 1 ture to ashigh as 170 C.

Table I.-Extreme pressure properties of lubricating oil compositionsdetermined as seizure and weld in the shell four ball machine (kilogramsof load) Compound A B C D E F Wt. percent additive in Seizure WeldSeizure Weld Seizure Weld Seizure Weld Seizure Weld Seizure Weld Plexol201:

0.0 110 55 110 55 110 55 110 55 110 0.3 75 160 05 140 1.0- 145 60 115 50130 5.0- 170 120 190 110 170 10.0- 110 225 110 170 Neutral:

0.0 45 45 110 45 110 45 110 45 110 45 110 1.0 100 175 110 70 140 70 5.0-l. 100 190 135 205 120 170 10.0. 100 220 175 345 110 210 HeavyIntermediate eutral: 0.0 65 125 65 125 65 125 65 125 65 125 65 125 1.0110 120 190 80 150 7 140 5.0- 90 310 110 210 130 10.0- 190 370 130 230 1Additive insoluble in base oil.

EXAMPLE 20 Dichlorobis-N,N-dibutylamylthioureazinc is prepared byreacting one mol of N-butylamylamine with 0.5 mol of carbon disulfideunder reflux conditions in the presence of toluene. The reaction productis then reacted with zinc chloride. The final reaction product isObtained by the procedures described hereinbefore.

EXAMPLE 21 Dichlorobis-N,N-dibutylhexylthioureazinc 2 4 9) ti 13)2:l2)

is prepared by reacting one mol (157 gms.) of N-butylhexylamine with 0.5mol (38 gms.) of carbon disulfide under reflux conditions in thepresence of toluene. 0.5 mol of the disubstituted thiourea product isthen reacted with 0.25 mol of zinc chloride. The final reaction productis obtained by the procedures previously described.

As has been previously indicated the organo-metallie compounds of thepresent invention unexpectedly provide extreme pressure characteristicsfor lubricating compositions when added to the same. It has been pointedout that the compounds of the present invention may be added to variousmineral and synthetic base stocks in amounts of from .05 to 15 weightpercent and preferably from 0.10 to 10.0% by weight. Lubricantcompositions prepared with varying amounts of these compounds In theforegoing table Plexol 201 is the synthetic lubricant (Z-EthylhexylSebacate manufactured by Rohm & Haas, Philadelphia, Penn. The 100Neutral is a base mineral oil having an API gravity of 32 (min.)specific gravity (max) 0.8654; flash COC F. (min.) 380; fire COC F.(min.) 430; viscositySUS at 100 F. 100410; at 210 F. 40; VI range (min.)95 and pour point F. (max) 0. The Heavy Intermediate base stock used hasthe following specification-API gravity 28 (min.), specific gravity(max) 0.8871; flash COC F. (min.) 510, fire COC F. (min.) 570;viscosity-SUS at 100 F. 632-7l2; at 210 F. 70-74; VI range (min.) 95 andpour point F. (max) 5.

Referring to Table I, it will be noted that the addition ofcomparatively small amounts of the new compounds of the presentinvention substantially improved in every instance the load carrying andextreme pressure characteristics of the lubricating composition to whichadded. For example, in the composition of 100 Neutral lubricating oil 1%of Compound C increased the seizure load more than 100% and the weldload approximately 50%. In a like manner the addition of Compound D to100 Neutral oil in the amount of 1% increased the seizure load over 100%and the Weld load approximately 35%. When increased to 5% by weightCompound D increased the load carrying property of 100 Neutral from 45to 135 and the weld load from 110 to 205. In substantially all othercases similar increases are to be noted.

In the examples which follow, representative samples of lubricantcompositions prepared with varying base materials including mixed basestocks and representative extreme pressure agents are set forth.

Dibromo bis N,N' dipropylamylthiourea cadmium product Example 19) In thetable which follows, data is set forth demonstrat ing the effectivenessof the additives of the present invention in lubricant compositionsprepared from mixtures of the additive and base stock materials.

Table lI.Tz'mken lubricant test [Conditions 110 F., 800 r.p.m.]

for the lubricant composition and the final characteristics desired inthe composition. Typical antiaoxidants which may be used for thispurpose are phenothiazine, phenylcz-naphthylamine,2,6-ditertiarybutyl-p-cresol and diphenyl-p-phenylenediamine. Suitableviscosity improvers in clude the following: polyacrylates,polyisobutylenes and polyvinyls. If a pour point depressant is desired,small amounts of one or more of the following materials may be added:condensation product of naphthalene and parafiin wax, polyacrylates andacrylate-vinyl copolymers.

While we have described our invention with some degree of particularitywith respect to the structures of the compounds and the method by whichthe compounds may be prepared, it is to be understood that we intend tolimit the same only in the manner provided by the claims appendedhereto.

We claim:

1. A lubricating composition having extreme pressure propertiescomprising a major amount of an oil base material and from about 0.05 toabout 15.0% by weight of a compound having the formula Percent OK loadScar Condition Base stock Additive additive (1b.) diam. of test block200 Neutral, 150

Bright Stock None 10 0.9 Pass. 37.5% 200 Neutral, 57

150 Bright Stock A 5 40 1. 62 Do.

Note.Additive A is diehlorobis-N,N'-dialkylthiourea zinc wherein thealkyl group is the miXtureC(CH3)2 1iHm-z3 (product Example 1).

Base stock Additive Percent No. of Scar Condition of additive teeth req.width in 60% Hvy. t. Neut., 40%

Lt. Int. Neut None 0 Sheared pin 59.75% Hvy. Int. Neut., at 750 p. s.i.39.75% Lt. Int. Neut A 0.5 0 0.3 No corrosion. 57.5% Hvy. Int. Neut.,

37.5% Lt. Int. Neut A 5 0 0.3 Do.

Table IV.Mac Coull corrosion test @350 F. 60 aralkyl having from 7 to 20carbon atoms and aryl and R" and R each represents a substituentselected from Base Stock Additive Pemqnt Bearing Acid the groupconsistmg of alkyl having from 3 to 20 carbon addltlv 1 a atoms,alicyclic having from 6 to 20 carbon atoms, amine substituted acyclichaving from 2 to 11 carbon atoms, 51 7; g g t, None 0 200 5 aralkylhaving from 7 to 20 carbon atoms and aryl. ,i I ];I53;j%" 2. Alubricating composition as claimed in claim 1 vy. Int. Neut A 0.6wherein X is chlorine, M is manganese, R and R are hy- In preparing thecompositions of the present invention, it may be desirable to improvecertain properties and characteristics of the composition by utilizingvarious known additives such as anti-oxidants, color stabilizers,viscosity improvers, pour point depressants, anti-foam agents anddetergents. These materials will be added in varying amounts dependingon the particular use intended 1 1 wherein X is chlorine, M is zinc, Rand R are hydrogen and R" and R' are C H NHC H N(CH 6. A lubricatingcomposition as claimed in claim 1 wherein X is iodine, M is cadmium, Rand R are hydrogen and R and R are C H 7. A mineral oil lubricatingcomposition having extreme pressure properties comprising a major amountof a mineral oil base material and from about 0.5% to about 15.0% byweight of a compound having the formula R or i l-R" M-S=C C R wherein Mis a metal selected from the group consisting of zinc, cadmium andmanganese, R and R each represents a substituent selected from the groupconsisting of hydrogen, alkyl having from 3 to 20 carbon atoms,alicyclic having from 6 to 20 carbon atoms, amine-substituted acyclichaving from 2 to 11 carbon atoms, aralkyl having from 7 to 20 carbonatoms and aryl and R and R' each represents a substituent selected fromthe group consisting of alkyl having from 3 to 20 carbon atoms,alicyclic having from 6 to 20 carbon atoms, amine-substituted acyclichaving from 2 to 11 carbon atoms, aralkyl having from 7 to 20 carbonatoms and aryl.

8. A mineral oil lubricating composition as claimed in claim 7 wherein Mis zinc, R and R are hydrogen and R and R are G l-I 9. A mineral oillubricating composition as claimed in claim 7 wherein M is zinc, R and Rare hydrogen and R and R are C H 10. A mineral oil lubricatingcomposition as claimed in claim 7 wherein M is manganese, R and R arehydrogen and R" and R are C H 11. A mineral oil lubricating compositionas claimed in claim 7 wherein M is zinc, R and R are Cid-I and R and Rare C l-I 12. A mineral oil lubricating composition as claimed in claim7 wherein M is zinc, R and R are hydrogen and R" and R are C I-I 13. Alubricating composition having extreme pressure properties comprising amajor amount of synthetic oil base stock and from about 0.05% to about15.0% by weight of a compound having the formula wherein M is a metalselected from the group consisting of zinc, cadmium and manganese, R andR each represents a substituent selected from the group consisting ofhydrogen, alkyl having from 3 to 20 carbon atoms, alicyclic having from6 to 20 carbon atoms, amine-substituted acyclic having from 2 to 11carbon atoms, aralkyl having from 7 to 20 carbon atoms and aryl and Rand R each represents a substituent selected from the group consistingof alkyl having from 3 to 20 carbon atoms, alicyclic having from 6 to 20carbon atoms, amine-substituted acyclic having from 2 to 11 carbonatoms, aralkyl having from 7 to 20 carbon atoms and aryl.

14. A lubricating composition comprising an oil base stock compositionas claimed in claim 13 wherein M is zinc, R and R are hydrogen and R andR are C H 15. A lubricating composition comprising an oil base stockcomposition as claimed in claim 14 wherein M is manganese, R and R arehydrogen and R and R' are C l-I 16. A lubricating composition comprisingan oil base stock composition as claimed in claim 15 wherein M is zinc,R and R are C H and R and R are C H 17. A lubricating composition havingextreme pressure properties comprising a major amount of an oil basematerial and from about 0.05% to about 15.0% by weight of an additivecontaining mixed alkyl compounds of the formula:

wherein each of R" and R is alkyl having from about 9 to about 11 carbonatoms, R and R' for each alkyl compound difiering from that of the otheralkylcompounds in said additive.

References Cited by the Examiner UNITED STATES PATENTS 12/33 Estabrooke260429 1,938,585 2,704,745 3/55 Kopp et al 252-475- 2,849,420 8/58Stevens et a1 260429 OTHER REFERENCES Engle et al.: B35712IVc/23c, June21, 1956 (German patent application).

DANIELE. WY MAN, Primary Examiner.

1. A LUBRICATING COMPOSITIO HAVING EXTREME PRESSURE PROPERTIESCOMPRISING A MAJOR AMOUNT OF AN OIL BASE MATERIAL AND FROM ABOUT 0.05 TOABOUT 15.0% BY WEIGHT OF A COMPOUND HAVING THE FORMULA